Soft-Hard Acid/Base-Controlled, Oxidative, N-Selective Arylation of Sulfonanilides via a Nitrenium Ion

Article abstract of DOI:10.1021/acs.joc.7b02841

In iodine(III)-catalyzed, dehydrogenative arylations of sulfonanilides, the functionalization of C-C bonds is preferred over the functionalization of C-N bonds. Herein, an unprecedented N-selective arylation of sulfonanilides using soft-hard acid-base (SHAB) control by a nitrenium ion over a carbenium ion is reported. Treatment of sulfonanilides with iodine(III) led to the formation of nitrenium ions (soft), which preferentially react with biphenyls (soft) over bimesityl (hard) to generate C-N bonds. The iodine(III) was generated in situ by using PhI and mCPBA at room temperature.

Full text of DOI:10.1021/acs.joc.7b02841

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Article
Soft-Hard Acid/Base-Controlled, Oxidative, N-
Selective Arylation of Sulfonanilides via a Nitrenium Ion
Saikat Maiti, and Prasenjit Mal
J. Org. Chem., Just Accepted Manuscript • Publication Date (Web): 05 Jan 2018
Downloaded from http://pubs.acs.org on January 5, 2018
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Soft-Hard Acid/Base-Controlled, Oxidative, N-Selective Arylation
of Sulfonanilides via a Nitrenium Ion
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Saikat Maiti and Prasenjit Mal*
School of Chemical Sciences, National Institute of Science Education and Research (NISER),
HBNI, Bhubaneswar, PO BhimpurꢀPadanpur, Via Jatni, District Khurda, Odisha 752050,
India
Abstract
In iodine (III)ꢀcatalyzed, dehydrogenative arylations of sulfonanilides, the functionalization
of CꢀC bonds is preferred over the functionalization of CꢀN bonds. Herein, an unprecedented
Nꢀselective arylation of sulfonanilides using softꢀhard acidꢀbase (SHAB) control by a
nitrenium ion over a carbenium ion is reported. Treatment of sulfonanilides with iodine (III)
led to the formation of nitrenium ions (soft), which preferentially react with biphenyls (soft)
over bimesityl (hard) to generate CꢀN bonds. The iodine (III) was generated in situ by using
PhI and mCPBA at room temperature.
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Introduction
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The development of new sustainable methods1 for CꢀN bond synthesis is of interests due to
the abundance of nitrogenous compounds in many synthetic intermediates, pharmaceutical
agents, natural products and biologically active molecules.2 Dehydrogenative CꢀN coupling
reactions3 by direct functionalization of CꢀH and NꢀH bonds are of great importance due to
their advantages of step and atom economy, not requiring prefunctionalization of the starting
materials, and so on.4 Many reports are available on transition metal catalyzed/mediated CꢀH
amination reactions;5 however, metalꢀfree hypervalent iodine (III) reagents are highly
efficient owing to their easy accessibility, low toxicity, high reactivity and safe handling.6 A
limited number of intermolecular CꢀH amination reactions using hypervalent iodine (III) are
known,7 and most of the reported reactions are based on carbonamide substrates and use
catalytic or (super) stoichiometric iodine (III) reagents.8 The use of either stoichiometric or
superꢀstoichiometric amounts of iodine (III) reagents can be disadvantageous because of the
generation of aryl iodide (ArI) byꢀproducts. Interestingly, a catalytic amount of ArI with an
appropriate oxidant could be used in place of the hypervalent iodine (III) reagents9 which
inspired us to develop conditions for generating iodine (III) in situ for the formation of CꢀN
bonds. To the best of our knowledge, there have been no reports on organocatalytic,
intermolecular, oxidative Nꢀarylations of sulfonanilides.
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Results and Discussion
The local environment can control the reactivity of certain chemical systems.10 Cooperative
multiple weak interactions11 like hydrophobic effects,12 chargeꢀtransfers,13 halogen bonding,14
cationꢀπ interactions,15 and anionꢀπ interactions16 are often explored in chemical synthesis.17
As a continuation of our research interest towards controlling the reactivity of nonꢀ
prefunctionalized aromatic systems18 by weak interactions,19 an unprecedented, Nꢀselective
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arylation of sulfonanilides via the regulation of the reactivity of a nitrenium ion20 over a
carbenium ion21 by softꢀhard acidꢀbase (SHAB) control is reported.22 Nitrenium ions are
wellꢀknown soft electrophiles23 whereas carbenium ions can be hard electrophiles because
when they are formed from the corresponding nitrenium ion, the aromaticity is broken
(Scheme 1a). Additionally, due to electron delocalization, the biphenyls or 1,2ꢀdiphenyl
acetylenes are expected to act as soft nucleophiles. Analogous to alkyl substituted arenes, the
bimesityl can behave like a hard nucleophile because of the restricted rotation between the
two aromatic rings (Scheme 1b).21 Through SHAB control,24 the competitive reactivity of the
nitrenium and carbenium ions is demonstrated herein (Scheme 1) for the oxidative, Nꢀ
selective arylation of sulfonanilides.
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Scheme 1. N-Arylation vs. C-Arylation by SHAB Control
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Scheme 2. Reactivity control at the N-center. a) Charge transfer control.13 b) N-
Arylation of heteroaromatics.7c c) Control by the lone pair at N-center
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a) Our earlier work: Contact-Explosive to Successful Chemical Reaction
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O
O
H
OAc
I
N
R1
NH2
H
OAc
+
NaHSO4
(acid salt)
Explosion Controller
PIDA
Contact Explosive
Explosion-Free CDC
up to 94 %
charge transfer control
b) Antonchick's work: N-Arylation on the Heteroaromatics
H
N
NH2
NH2
-H+
Ph
iodine(III)
I
Induced
+R effect
OAc
N
N
N
R1
R1
R1
non-directional, weak interaction
Hard electrophile
c) Strategy: Intramolecular Control at N-Center for N-Arylation
NHSO2R
SO2R
N
-AcOH
H
N
iodine(III)
n
SO
S
O
R1
O
R1
lone pair protected, less reactive
Soft electrophile
Sulfonanilides are an important class of synthetic scaffolds in organic synthesis. Due to the
strong electronꢀwithdrawing effect of the attached sulfonyl group, sulfonanilides have a
unique reactivity towards hypervalent iodine (III) reagents25 over carbonamides.26 Couplings
between sulfonanilides and aromatic substrates were first demonstrated by Canesi and coꢀ
workers who documented the formation of a nitrenium ion.27 In addition, the reactivity of the
Nꢀcenter can be controlled either intraꢀ or intermolecularly. We have previously reported a
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successful cross dehydrogenative coupling (CDC) reaction using contact explosives, primary
amines, and phenyliodine (III) diacetate (PIDA) under maximum contact between the
reactants, i.e., solventꢀfree conditions.13 The charge transfer basicity of the amine was
controlled using an acidic salt, NaHSO4 (Scheme 2a). Antonchick’s Nꢀarylation of
heteroaromatics is shown in Scheme 2b,7c and the pyridinium nitrogen center may have
reduced the reactivity of PIDA. The absence of an electronꢀwithdrawing group on the amine
results in the formation of a highly reactive nitrenium ion that can be considered a hard
electrophile. Thus, the reactivity of the nitrenium ion was found to be selective with hard
arene nucleophiles. Moreover, due to the n→π*SO interaction, the loneꢀpair of the
sulfonanilide nitrogen was protected and led to a softer electrophile for Nꢀarylation.19a Due to
the presence of electronꢀdonating ꢀMe groups and restricted electron mobility between the
two aromatic rings, the bimesityl is anticipated to be a relatively harder nucleophile. This
hypothesis was successfully proved when the Cꢀarylated product was exclusively isolated
from the reaction of sulfonanilide and bimesityl under the standard reaction conditions (vide
infra).
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The reactivity of sulfonanilides in selective NꢀH arylation with arenes under conditions that
generate hypervalent iodine (III) in situ is shown. The iodine (III) was generated using PhI
28
(30 mol %) and metaꢀchloroperbenzoic acid (mCPBA) as the oxidant.9b,
At room
temperature, one C(sp2)ꢀH and one N(sp3)ꢀH were functionalized in the intermolecular
dehydrogenative CꢀN bond formation. We have previously demonstrated an intermolecular
annulation between sulfonanilides and arenes for the synthesis of carbazoles in which the Cꢀ
H arylation of the sulfonanilides was established as the intermediate step. CꢀH Arylation
reactions with alkylꢀ or alkoxyꢀsubstituted arenes were found to occur via a nitrenium ion.21
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Table 1. Optimization of the Methoda
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entry
ArI (mol%)
oxidant
solvent
3a (%)b
(1.5 equiv)
1
2
3
4
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6
7
8
PhI (30)
PhI (30)
mCPBA
mCPBA
HFIP
TFE
83
69
35
75
77
27
66
87
4ꢀNO2ꢀC6H4ꢀI (30) mCPBA
4ꢀMeꢀC6H4ꢀI (30) mCPBA
HFIP
HFIP
HFIP
DCM
ACN
PhI (20)
PhI (30)
PhI (30)
PhI (30)
mCPBA
mCPBA
mCPBA
mCPBA
HFIP/DCM
(2:1)
9
PhI (30)
PhI (30)
DTBP
TBHP
HFIP
HFIP
NR
NR
10
aUnless noted otherwise, 1.5 equiv of 2a was used. bIsolated Yields
.
During the optimization of the reaction conditions, Nꢀ(4ꢀbromophenyl)methanesulfonamide
(1a) and biphenyl (2a) were used as the model substrates. The optimal conditions for the
reaction were determined in the presence of 30 mol % of iodobenzene (PhI) and 1.5 equiv of
oxidant (mCPBA) over 6 h in 1,1,1,3,3,3ꢀhexafluoroꢀ2ꢀpropanol (HFIP)ꢀdichloromethane
(DCM) (2:1) at room temperature. The product (3a) was isolated in a satisfactory yield of
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87% (Table 1, entry 8). However, the yield was reduced to 83% in pure HFIP (Table 1, entry
1). When using 2,2,2ꢀtrifluoroethanol (TFE) as the only solvent, the product formation
noticeably dropped to 69% (Table 1, entry 2). Use of other solvents such as dichloromethane
(DCM) and acetonitrile (ACN) yielded inferior results (Table 1, entries 6 and 7). Aryl iodides
with electronꢀwithdrawing as well as with electronꢀdonating groups also led to inferior results
(Table 1, entries 3 and 4). No desired product could be isolated when either diꢀtertꢀbutyl
peroxide (DTBP) or tertꢀbutyl hydroperoxide (TBHP) were used as oxidants (Table 1, entries
9 and 10). Reducing the loading of iodobenzene to 20 mol % led to poorer results (Table 1,
entry 5). The use of 1.5 equiv of biphenyl with respect to the sulfonanilide substrate was
identified as the optimum stoichiometry for the reaction. Under the optimized conditions,
along with the desired diarylamine, a trace amount (6%) of a minor product, carbazole
derivative 3a', was isolated as well.
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The scope of the Nꢀarylation reaction by sulfonanilides is shown in Scheme 3, and the desired
diarylamines were isolated in good yields. Halides as well as phenyl groups containing
sulfonanilides were wellꢀtolerated (3a-g, 3o, and 3r). Electronꢀwithdrawing anilides
containing ꢀCOPh, ꢀNO2, and ꢀCN groups were not completely consumed during the reaction
and resulted in lower yields of the corresponding products (3n and 3p-q). Diarylamines from
sulfonanilide substrates containing electronꢀdonating groups were also isolated in reasonable
yields (3b, 3h-m, and 3s-u). Steric effects were one reasons for the low yields of certain
substrates (3j-k and 3n). Furthermore, anilides bearing different sulfonyl groups, such as –
SO2Ph, ꢀTs, and ꢀNs, were also found to be efficient in the oxidative CꢀN coupling protocol
(3r-u). The structure of compound 3a was characterized by Xꢀray crystallographic analysis.
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Scheme 3. N-Arylation with biphenyls
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Scheme 4. a) Control experiment. b) 1,2-Diphenylethyne as a nucleophile
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a) Control experiment with a hard nucleophile
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MsHN
NHMs
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standard condition
+
I
I
4, 77%
2c
1d
b) The effect of a soft nucleophile
SO2R
SO2R
H
PhI (30 mol %)
mCPBA (1.5 equiv)
N
N
H
+
HFIP-DCM (2:1)
rt, 6 h
R1
R1
Ph
Ph
Ph
1 (0.5 mmol)
3
2b (0.75 mmol)
SO2Ph
N
Ms
N
Ms
N
I
I
Br
Ph
3aa, 74%
Ph
3ac, 66%
3ab, 78%
The control experiment shown in Scheme 4a proved that the Cꢀarylated product was formed
due to the hardness of the bimesityl nucleophile, and 4 was isolated in 77% yield. However,
the use of diphenylacetylene (2b) as the arene nucleophile (soft) in the arylation reaction led
to Nꢀarylated diarylamines in good yields (Scheme 4b, 3aa-3ac).
In this study, biphenyl and diphenylacetylene were reacted with different sulfonanilides to
generate Nꢀarylated products. We have already shown that alkylꢀ or alkoxyꢀsubstituted arenes
lead to Cꢀarylated products.21 As a limitation of this methodology, attempts to use
diphenylacetylenes with substitutions at the 4ꢀ and 4’ꢀpositions were unsuccessful. No other
substituted biphenyl substrates were tested in the current protocol.
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Scheme 5. Plausible mechanism
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A plausible mechanism for the intermolecular dehydrogenative CꢀN coupling reaction is
proposed in Scheme 5. A trivalent iodine (III) species (either PhIO or PhI(OCOPh)2) is
expected to be formed in situ during the reaction of the oxidant (mCPBA) and the iodoarene
with the concomitant generation of mCBA.28d Subsequently, the interaction of the
29
sulfonanilide and the iodine (III) species is expected to generate nitrenium ion20a,
intermediate 5. Depending on the nature of the nucleophiles available in the reaction system,
the softer nitrenium ion can be converted to a harder carbenium ion by loss of aromatic ring
current via resonance. Similarly, because of the extended delocalization of the electrons in the
biphenyls or diphenyl acetylenes, they become softer nucleophiles. Therefore, due to the
preference of soft for soft, the Nꢀarylation was favored over the Cꢀarylation. Finally, the
nucleophilic attack from arene (2) onto the electron deficient Nꢀcenter led to the formation of
another carbenium ion intermediate (6), which subsequently was transformed into the
corresponding diarylamine product (3) by the abstraction of one proton by either HOꢀ or
PhOCOꢀ. Substituents on the aryl ring of the sulfonanilides could determine the stability of
ionic species 5; thus, poor yields from anilides bearing stronger electronꢀwithdrawing groups
(Scheme 3, 3n and 3p-q) were observed. The isolation of trace amounts of carbazoles in
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certain cases could be explained by the Cꢀarylation step occurring first (through a carbenium
intermediate) followed by CꢀN bond formation as previously reported.21
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Conclusions
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In summary, we herein report a unique protocol for selective NꢀH arylation over CꢀH
arylation of sulfonanilides using hypervalent iodine (III). The iodine (III) species was
generated in situ from PhI and mCPBA. Overall, an intermolecular, dehydrogenative CꢀN
bond formation reaction for the construction of diphenylamines from nonꢀprefunctionalized
substrates was established under mild, metalꢀfree conditions. We anticipate that this
intermolecular NꢀH arylation method might lead to a powerful approach to the synthesis of
diarylamine compounds.30 The ability to control the reactivity of the NꢀH arylation reaction
using the principles of SHAB can have important applications in supramolecular catalysis.31
EXPERIMENTAL SECTION
General Methods. Column chromatographic purifications of the synthesized compounds
were performed using silica gel (mesh 230ꢀ400) and hexaneꢀethyl acetate mixtures as eluents
unless otherwise specified. NMR spectra were recorded on a 400 MHz instrument at 25 °C.
The chemical shift values are reported in parts per million (ppm) with respect to residual
chloroform (7.26 ppm for 1H and 77.16 for 13C). Data are reported as follows: chemical shift
in ppm (δ), multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, brs = broad singlet,
and m = multiplet), coupling constant (Hz) and integration. Highꢀresolution mass spectra
(HRꢀMS) were recorded on an ESIꢀTOF (time of flight) mass spectrometer. Infrared spectral
data are reported in wave numbers (cmꢀ1). Melting points of the compounds were determined
using a digital melting point apparatus and are uncorrected. FTꢀIR spectra were recorded after
forming a thin layer of the target compound on the surface of a NaCl crystal using
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dichloromethane. Thinꢀlayer chromatography (TLC) was performed on Merck Silica Gel
F254 plates (0.25 mm). The spots and bands were visualized using 254 nm UV light.
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Materials. Iodobenzene (PhI) and mꢀchloroperbenzoic acid (mCPBA) were purchased from
commercial source and used without further purification. Sulfonanilides were prepared by the
reaction of commercially available anilines and sulfonyl chlorides in the presence of pyridine
in dichloromethane (DCM) as the solvent.32
Representative procedure for the preparation of N-([1,1'-biphenyl]-4-yl)-N-(4-
bromophenyl)methanesulfonamide (3a). To
a
stirred solution of Nꢀ(4ꢀ
bromophenyl)methanesulfonamide (1a, 250 mg, 1.0 mmol), 1,1'ꢀbiphenyl (2a, 231 mg, 1.5
mmol) and iodobenzene (33 µL, 0.3 mmol) in 1,1,1,3,3,3ꢀhexafluoroisopropanol (HFIP,
(CF3)2CHOH) – dichloromethane (DCM, CH2Cl2) (2:1, 4.5 mL) was added mCPBA (259
mg, 1.5 mmol) in one portion under ambient conditions, and the mixture was allowed to stir
for 6 h at room temperature. The progress of the reaction was monitored by TLC using a
mixture of hexane and ethyl acetate as the eluent. After completion, the solvent was
evaporated and a saturated aqueous solution of NaHCO3 was added. The aqueous phase was
extracted with ethyl acetate. The organic phase was dried over anhydrous Na2SO4, and the
resulting solution was evaporated to dryness. The residue was purified by column
chromatography on silica gel to give pure Nꢀ([1,1'ꢀbiphenyl]ꢀ4ꢀyl)ꢀNꢀ(4ꢀ
bromophenyl)methanesulfonamide (3a) as the major product (350 mg white solid, 0.87
mmol, yield 87%).
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N-([1,1'-Biphenyl]-4-yl)-N-(4-bromophenyl)methanesulfonamide (3a): Rf
=
0.45
4
5
6
1
(hexane:ethyl acetate 4:1); white solid; yield 87% (350 mg); mp 150ꢀ152 °C; H NMR (400
7
8
MHz, CDCl3): δ 7.60 (d, J = 8 Hz, 2H), 7.57ꢀ7.50 (m, 4H), 7.46ꢀ7.41 (m, 4H), 7.38 (d, J = 8
Hz, 1H), 7.29 (d, J = 8 Hz, 2H), 3.18 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 140.7, 140.5,
9
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60
~
140.0, 139.9, 132.8, 129.0, 128.4, 127.9, 127.9, 127.2, 121.1, 40.2; IR (KBr):
ν
= 3024,
2927, 1509, 1337, 1152 cmꢀ1; HRꢀMS (ESIꢀTOF): m/z calculated for C19H16NO2SBrNa [M +
Na]+: 423.9977, found: 423.9962.
N-([1,1'-Biphenyl]-4-yl)-N-(4-bromo-3-methylphenyl)methanesulfonamide (3b): Rf
=
0.55 (hexane:ethylacetate 4:1); white solid; yield 75% (140 mg); mp 98ꢀ99 °C; 1H NMR (400
MHz, CDCl3): δ 7.60ꢀ7.53 (m, 5H), 7.46ꢀ7.42 (m, 4H), 7.38ꢀ7.36 (m, 1H), 7.29ꢀ7.27 (m, 1H),
7.13ꢀ7.11 (m,1H), 3.18 (s, 3H), 2.39 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 140.5, 140.4,
140.2, 140.0, 139.7, 133.4, 130.0, 129.0, 128.4, 127.8, 127.7, 127.2, 126.5, 123.9, 40.2, 23.2;
ꢀ1
~
IR (KBr):
ν
= 3031, 2927, 1515, 1347, 1156 cm ; HRꢀMS (ESIꢀTOF): m/z calculated for
C20H18NO2SBrNa [M + Na]+: 438.0134, found: 438.0118.
N-([1,1'-Biphenyl]-4-yl)-N-(4-chlorophenyl)methanesulfonamide (3c): Rf
=
0.60
1
(hexane:ethylacetate 4:1); white solid; yield 79% (206 mg); mp 151ꢀ153 °C; H NMR (400
MHz, CDCl3): δ 7.61ꢀ7.59 (m, 2H), 7.57ꢀ7.54 (m, 2H), 7.46ꢀ7.42 (m, 4H), 7.38ꢀ7.36 (m, 5H),
3.18 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 140.7, 140.1, 139.9, 139.9, 133.3, 129.9, 129.8,
~
129.0, 128.8, 128.4, 127.8, 127.2, 122.3, 40.2; IR (KBr):
ν
= 3030, 2926, 1512, 1346, 1156
cmꢀ1; HRꢀMS (ESIꢀTOF): m/z calculated for C19H16NO2SClNa [M + Na]+: 380.0482, found:
380.0491.
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N-([1,1'-Biphenyl]-4-yl)-N-(4-iodophenyl)methanesulfonamide (3d): Rf
=
0.55
4
5
6
7
8
(hexane:ethylacetate 4:1); white solid; yield 83% (139 mg); (isolated yield 67% when 0.75
1
equiv of biphenyl was used instead of 1.5 equiv) mp 158ꢀ160 °C; H NMR (400 MHz,
9
CDCl3): δ 7.71 (d, J = 8 Hz, 2H), 7.6ꢀ7.55 (m, 4H), 7.47ꢀ7.41 (m, 4H), 7.39ꢀ7.35 (m, 1H),
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59
60
7.16 (d, J = 8 Hz, 2H), 3.18 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 141.2, 140.7, 139.9,
~
139.9, 138.8, 129.1, 129.0, 128.4, 128.0, 127.8, 127.2, 92.2, 40.2; IR (KBr):
ν
= 3096, 2933,
1513, 1346, 1156 cmꢀ1; HRꢀMS (ESIꢀTOF): m/z calculated for C19H16NO2SINa [M + Na]+:
471.9839, found: 471.9836.
N-([1,1'-Biphenyl]-4-yl)-N-(4-fluorophenyl)methanesulfonamide (3e): Rf
=
0.35
1
(hexane:ethylacetate 9:1); white solid; yield 58% (84 mg); mp 186ꢀ188 °C; H NMR (400
MHz, CDCl3): δ 7.60ꢀ7.54 (m, 4H), 7.46ꢀ7.41 (m, 6H), 7.38ꢀ7.34 (m, 1H), 7.12ꢀ7.07 (m, 2H),
1
3.18 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 161.85 (d, JC,F = 247 Hz), 140.5, 140.4, 140.0,
4
3
137.16 (d, JC,F = 3 Hz), 130.1 (d, JC,F = 9 Hz), 129.0, 128.4, 127.8, 127.4, 127.2, 116.6 (d,
ꢀ1
2JC,F = 23 Hz), 40.1; IR (KBr):
ν
= 3072, 2927, 1503, 1334, 1144 cm ; HRꢀMS (ESIꢀTOF):
~
m/z calculated for C19H16NO2SFNa [M+Na]+: 364.0778, found: 364.0790.
N-([1,1'-Biphenyl]-4-yl)-N-(3-chloro-4-fluorophenyl)methanesulfonamide (3f): Rf = 0.40
1
(hexane:ethylacetate 9:1); white solid; yield 55% (102 mg); mp 145ꢀ147 °C; H NMR (400
MHz, CDCl3): δ 7.61 (d, J = 8 Hz, 2H), 7.56 (d, J = 8 Hz, 2H), 7.50ꢀ7.46 (m, 1H), 7.45ꢀ7.41
(m, 4H), 7.39ꢀ7.31 (m, 2H), 7.17 (t, J = 8 Hz, 1H), 3.19 (s, 3H); 13C NMR (100 MHz, CDCl3)
1
4
3
δ 157.3 (d, JC,F = 249 Hz), 140.9, 139.9 (d, JC,F = 3 Hz), 137.7 (d, JC,F = 4 Hz), 130.1,
2
129.0, 128.6, 127.9, 127.9, 127.8, 127.8, 127.2, 121.9 (d, JC,F = 19 Hz), 117.3 (d, 2JC,F = 22
ꢀ1
~
Hz), 40.3; IR (KBr):
ν
= 3097, 2931, 1494, 1348, 1158 cm ; HRꢀMS (ESIꢀTOF): m/z
calculated for C19H16NO2SClF [M + H]+: 376.0569, found: 376.0554.
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N-([1,1'-Biphenyl]-4-yl)-N-(3,4-dichlorophenyl)methanesulfonamide (3g): Rf = 0.45
1
(hexane:ethylacetate 9:1); white solid; yield 56% (116 mg); mp 130ꢀ131 °C; H NMR (400
9
MHz, CDCl3): δ 7.63 (d, J = 8 Hz, 2H), 7.57 (d, J = 8 Hz, 2H), 7.51 (s, 1H), 7.48ꢀ7.38 (m,
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6H), 7.29ꢀ7.26 (m, 1H), 3.20 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 141.2, 140.8, 139.8,
139.5, 133.4, 131.3, 131.1, 129.0, 128.7, 128.6, 128.3, 127.9, 127.2, 126.3, 40.3; IR (KBr):
~
ν
= 3031, 2932, 1485, 1349, 1160 cmꢀ1; HRꢀMS (ESIꢀTOF): m/z calculated for
C19H16NO2SCl2 [M + H]+: 392.0273, found: 392.0274.
N-([1,1'-Biphenyl]-4-yl)-N-(p-tolyl)methanesulfonamide
(3h):
Rf
=
0.40
1
(hexane:ethylacetate 9:1); white solid; yield 61% (140 mg); mp 178ꢀ180 °C; H NMR (400
MHz, CDCl3): δ 7.58ꢀ7.54 (m, 4H), 7.45ꢀ7.41 (m, 4H), 7.37ꢀ7.32 (m, 3H), 7.21 (d, J = 8 Hz,
2H), 3.18 (s, 3H), 2.36 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 140.8, 140.1, 140.0, 138.6,
~
137.9, 130.4, 128.9, 128.2, 128.1, 127.7, 127.3, 127.2, 40.1, 21.1; IR (KBr):
ν
= 3030, 2925,
1510, 1485, 1339, 1155 cmꢀ1; HRꢀMS (ESIꢀTOF): m/z calculated for C20H19NO2SNa [M +
Na]+: 360.1029, found: 360.1058.
N-([1,1'-Biphenyl]-4-yl)-N-(4-ethylphenyl)methanesulfonamide (3i): Rf
=
0.35
1
(hexane:ethylacetate 19:1); white solid; yield 63% (160 mg); mp 98ꢀ100 °C; H NMR (400
MHz, CDCl3): δ 7.59ꢀ7.54 (m, 4H), 7.46ꢀ7.42 (m, 4H), 7.37ꢀ7.34 (m, 3H), 7.24 (d, J = 8 Hz,
2H), 3.18 (s, 3H), 2.67 (q, J = 8 Hz, 2H), 1.25 (t, J = 8 Hz, 3H); 13C NMR (100 MHz,
CDCl3): δ 144.0, 140.8, 140.1, 140.0, 138.7, 129.2, 128.9, 128.2, 128.1, 127.7, 127.4, 127.2,
ꢀ1
~
40.1, 28.5, 15.4; IR (KBr):
ν
= 3031, 2931, 1509, 1486, 1346, 1157 cm ; HRꢀMS (ESIꢀ
TOF): m/z calculated for C21H22NO2S [M + H]+: 352.1366, found: 352.1361.
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N-([1,1'-Biphenyl]-4-yl)-N-(2,4-dimethylphenyl)methanesulfonamide (3j): Rf = 0.40
4
5
6
1
(hexane:ethylacetate 9:1); white solid; yield 49% (100 mg); mp 94ꢀ96 °C; H NMR (400
7
8
9
MHz, CDCl3): δ 7.55ꢀ7.53 (m, 4H), 7.45ꢀ7.41 (m, 4H), 7.36ꢀ7.33 (m, 2H), 7.14ꢀ7.11 (m, 2H),
3.20 (s, 3H), 2.36 (s, 3H), 2.35 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 140.3, 140.1, 139.1,
138.6, 138.6, 136.4, 132.7, 129.5, 128.9, 128.0, 127.9, 127.5, 127.0, 124.6, 40.1, 21.2, 18.6;
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46
47
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58
59
60
ꢀ1
~
IR (KBr):
ν
= 3030, 2925, 1485, 1345, 1152 cm ; HRꢀMS (ESIꢀTOF): m/z calculated for
C21H22NO2S [M + H]+: 352.1366, found: 352.1370.
N-([1,1'-Biphenyl]-4-yl)-N-mesitylmethanesulfonamide
(3k):
Rf
=
0.40
1
(hexane:ethylacetate 9:1); semi solid; yield 45% (116 mg); H NMR (400 MHz, CDCl3): δ
7.55ꢀ7.51 (m, 4H), 7.43 (t, J = 8 Hz, 2H), 7.33 (t, J = 8 Hz, 1H), 7.25 (d, J = 8 Hz, 2H), 7.00
(s, 2H), 3.32 (s, 3H), 2.33 (s, 3H), 2.28 (s, 6H); 13C NMR (100 MHz, CDCl3): δ 140.1, 139.0,
~
138.7, 136.4, 134.5, 130.1, 128.9, 128.1, 127.3, 126.9, 119.2, 40.3, 21.2, 19.1; IR (KBr):
ν =
3031, 2923, 1517, 1485, 1342, 1157 cmꢀ1; HRꢀMS (ESIꢀTOF): m/z calculated for
C22H23NSO2Na [M + Na]+: 388.1342, found: 388.1313.
N-([1,1'-Biphenyl]-4-yl)-N-(4-isopropylphenyl)methanesulfonamide (3l): Rf
=
0.45
1
(hexane:ethylacetate 9:1); white solid; yield 70% (60 mg); mp 114ꢀ116 °C; H NMR (400
MHz, CDCl3): δ 7.58ꢀ7.53 (m, 4H), 7.46ꢀ7.41 (m, 4H), 7.37ꢀ7.33 (m, 3H), 7.26ꢀ7.24 (m, 1H),
3.18 (s, 3H), 2.91 (sept, J = 8 Hz, 1H), 1.24 (d, J = 4 Hz, 6H); 13C NMR (100 MHz, CDCl3):
δ 148.6, 140.8, 140.2, 140.1, 138.7, 128.9, 128.2, 128.0, 127.8, 127.7, 127.6, 127.2, 40.1,
ꢀ1
~
33.8, 24.0; IR (KBr):
ν
= 3031, 2960, 1508, 1486, 1347, 1157 cm ; HRꢀMS (ESIꢀTOF):
m/z calculated for C22H23NO2SNa [M + Na]+: 388.1342, found: 388.1339.
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N-([1,1'-Biphenyl]-4-yl)-N-(4-(tert-butyl)phenyl)methanesulfonamide (3m): Rf = 0.45
4
5
6
1
(hexane:ethylacetate 9:1); white solid; yield 63% (105 mg); mp 142ꢀ144 °C; H NMR (400
7
8
9
MHz, CDCl3): δ 7.59ꢀ7.54 (m, 4H), 7.46ꢀ7.39 (m, 6H), 7.37ꢀ7.33 (m, 3H), 3.19 (s, 3H), 1.31
(s, 9H); 13C NMR (100 MHz, CDCl3): δ 150.8, 140.7, 140.2, 138.5, 128.9, 128.2, 127.7,
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43
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47
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53
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56
57
58
59
60
ꢀ1
~
127.5, 127.2, 126.7, 40.1, 34.7, 31.4; IR (KBr):
ν
= 3031, 2962, 1486, 1347, 1158 cm ; HRꢀ
MS (ESIꢀTOF): m/z calculated for C23H26NO2S [M + H]+: 380.1679, found: 380.1665.
N-([1,1'-Biphenyl]-4-yl)-N-(2-benzoyl-4-chlorophenyl)methanesulfonamide (3n): Rf =
1
0.30 (hexane:ethylacetate 9:1); semiꢀsolid; yield 50% (88 mg); H NMR (400 MHz, CDCl3):
δ 7.71 (d, J = 8 Hz, 2H), 7.61 (d, J = 8 Hz, 1H), 7.55ꢀ7.50 (m, 1H), 7.46ꢀ7.38 (m, 11H), 7.36ꢀ
7.33 (m, 2H), 3.06 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 194.8, 140.2, 140.1, 140.1, 140.0,
137.9, 136.1, 133.8, 133.3, 132.8, 131.5, 130.6, 129.6, 128.9, 128.5, 128.1, 127.7, 127.7,
ꢀ1
~
127.2, 40.64; IR (KBr):
ν
= 3031, 2925, 1668, 1516, 1485, 1349, 1157cm ; HRꢀMS (ESIꢀ
TOF): m/z calculated for C26H20NO3SClNa [M + Na]+: 484.0745, found: 484.0736.
N,N-di([1,1'-Biphenyl]-4-yl)methanesulfonamide (3o): Rf = 0.45 (hexane:ethylacetate 9:1);
1
white solid; yield 76% (122 mg); mp 170ꢀ172 °C; H NMR (400 MHz, CDCl3): δ7.63ꢀ7.56
(m, 8H), 7.51ꢀ7.43 (m, 8H), 7.39ꢀ7.35 (m, 2H), 3.23 (s, 3H); 13C NMR (100 MHz, CDCl3): δ
~
140.5, 140.4, 140.1, 129.0, 128.4, 127.9, 127.8, 127.2, 40.25; IR (KBr):
ν = 3031, 2933,
1513, 1486, 1342, 1148cmꢀ1; HRꢀMS (ESIꢀTOF): m/z calculated for C25H21NO2SNa [M +
Na]+: 422.1185, found: 422.1207.
N-([1,1'-Biphenyl]-4-yl)-N-(4-cyanophenyl)methanesulfonamide (3p): Rf
=
0.35
1
(hexane:ethylacetate 4:1); white solid; yield 35% (44 mg); mp 180ꢀ182 °C; H NMR (400
MHz, CDCl3): δ 7.68ꢀ7.65 (m, 2H), 7.64ꢀ7.61 (m, 2H), 7.59ꢀ7.57 (m, 2H), 7.48ꢀ7.37 (m, 7H),
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3.23 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 145.8, 141.9, 139.6, 138.6, 133.4, 129.4, 129.1,
~
128.8, 128.1, 127.2, 124.6, 118.3, 109.1, 40.32; IR (KBr):
ν
= 3031, 2932, 2229, 1601,
6
1502, 1485, 1350, 1158 cmꢀ1; HRꢀMS (ESIꢀTOF): m/z calculated for C20H16N2O2S [M + H]+:
349.1005, found: 349.1020.
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8
9
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N-([1,1'-Biphenyl]-4-yl)-N-(4-nitrophenyl)methanesulfonamide (3q): Rf
=
0.40
1
(hexane:ethylacetate 4:1); white solid; yield 33% (31 mg); mp 194ꢀ196 °C; H NMR (400
MHz, CDCl3): δ 8.20 (d, J = 8 Hz, 2H), 7.69 (d, J = 12 Hz, 2H), 7.59 (d, J = 8 Hz, 2H), 7.49ꢀ
7.38 (m, 7H), 3.25 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 147.6, 144.6, 142.2, 139.6, 138.5,
~
129.6, 129.1, 129.0, 128.2, 127.3, 125.0, 123.8, 40.3; IR (KBr):
ν = 3031, 2933, 1590, 1515,
1486, 1344, 1112 cmꢀ1; HRꢀMS (ESIꢀTOF): m/z calculated for C19H17N2O4S [M + H]+:
369.0904, found: 369.0894.
N-([1,1'-Biphenyl]-4-yl)-N-(4-bromophenyl)benzenesulfonamide (3r): Rf
=
0.50
1
(hexane:ethylacetate 9:1); white solid; yield 78% (116 mg); mp 168ꢀ170 °C; H NMR (400
MHz, CDCl3): δ 7.74 (d, J = 8 Hz, 2H), 7.62 (t, J = 8 Hz, 1H), 7.56ꢀ7.49 (m, 6H), 7.47ꢀ7.42
(m, 4H), 7.38ꢀ7.34 (m, 1H), 7.30 (d, J = 8 Hz, 2H), 7.18 (d, J = 8 Hz, 2H); 13C NMR (100
MHz, CDCl3): δ 140.8, 140.6, 140.3, 140.2, 140.0, 133.2, 132.6, 129.8, 129.2, 129.0, 128.6,
ꢀ1
~
128.2, 127.8, 127.8, 127.2, 121.5; IR (KBr):
ν
= 3031, 2924, 1513, 1485, 1355, 1164 cm ;
HRꢀMS (ESIꢀTOF): m/z calculated for C24H19NO2SBr [M + H]+: 464.0314, found: 464.0300.
N-([1,1'-Biphenyl]-4-yl)-N-(4-(tert-butyl)phenyl)benzenesulfonamide (3s): Rf = 0.45
1
(hexane:ethylacetate 9:1); white solid; yield 67% (96 mg); mp 154ꢀ156 °C; H NMR (400
MHz, CDCl3): δ7.76 (d, J = 8 Hz, 2H), 7.61 (t, J = 8 Hz, 1H), 7.55ꢀ7.48 (m, 6H), 7.43 (t, J =
8 Hz, 2H), 7.36ꢀ7.32 (m, 5H), 7.21 (d, J = 8 Hz, 2H), 1.30 (s, 9H); 13C NMR (100 MHz,
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CDCl3): δ 150.8, 140.8, 140.8, 140.4, 140.2, 138.7, 132.8, 129.0, 128.9, 128.6, 128.0, 128.0,
~
127.9, 127.7, 127.2, 126.4, 34.7, 31.4; IR (KBr):
ν
= 3031, 2903, 1510, 1486, 1355, 1166
6
cmꢀ1; HRꢀMS (ESIꢀTOF): m/z calculated for C28H27NSO2Na [M + Na]+: 464.1655, found:
464.1650.
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60
N-([1,1'-Biphenyl]-4-yl)-4-methyl-N-(p-tolyl)benzenesulfonamide (3t): Rf
=
0.55
1
(hexane:ethylacetate 9:1); white solid; yield 70% (165 mg); mp 148ꢀ150 °C; H NMR (400
MHz, CDCl3): δ 7.62 (d, J = 8 Hz, 2H), 7.54ꢀ7.50 (m, 4H), 7.42 (t, J = 8 Hz, 2H), 7.36ꢀ7.32
13
(m, 3H), 7.28 (d, J = 8 Hz, 2H), 7.19ꢀ7.12 (m,4H), 2.44 (s, 3H), 2.33 (s, 3H); C NMR (100
MHz, CDCl3): δ 143.7, 141.1, 140.2, 140.1, 138.9, 137.8, 137.8, 130.1, 129.6, 128.9, 128.6,
~
128.2, 128.0, 127.9, 127.6, 127.2, 21.7, 21.2; IR (KBr):
ν = 3047, 2923, 1511, 1485, 1351,
1158 cmꢀ1; HRꢀMS (ESIꢀTOF): m/z calculated for C26H24NO2S [M + H]+: 414.1522, found:
414.1510.
N-([1,1'-Biphenyl]-4-yl)-N-(4-bromophenyl)-4-nitrobenzenesulfonamide (3u): Rf = 0.50
1
(hexane:ethylacetate 10:1); white solid; yield 42% (54 mg); mp 138ꢀ140 °C; H NMR (400
MHz, CDCl3): δ 8.36 (d, J = 8 Hz, 2H), 7.91 (d, J = 8 Hz, 2H), 7.57ꢀ7.53 (m, 4H), 7.50ꢀ7.44
(m, 5H), 7.28 (d, J = 8 Hz, 2H), 7.17 (d, J = 8 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ
150.4, 145.8, 141.5, 139.9, 139.7, 139.5, 132.9, 129.8, 129.1, 128.6, 128.5, 128.1, 127.2,
ꢀ1
~
127.1, 124.5, 122.3; IR (KBr):
ν
= 3031, 2923, 1528, 1484, 1348, 1164cm ; HRꢀMS (ESIꢀ
TOF): m/z = calculated for C24H17BrN2O4SNa [M + Na]+: 530.9984, found: 530.9969.
N-(4-Bromophenyl)-N-(4-(phenylethynyl)phenyl)methanesulfonamide (3aa): Rf = 0.50
1
(hexane:ethylacetate 9:1); white solid; yield 74% (76 mg); mp 197ꢀ198 °C; H NMR (400
MHz, CDCl3): δ 8.08 (d, J = 8 Hz, 1H), 7.73ꢀ7.72 (m, 1H), 7.53ꢀ7.50 (m, 1H), 7.38ꢀ7.27 (m,
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8H), 7.19ꢀ7.17 (m, 2H), 2.89 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 137.9, 135.6, 132.0,
131.9, 131.8, 130.3, 129.9, 129.2, 128.6, 128.4, 127.9, 127.5, 123.8, 123.0, 118.1, 117.1,
ꢀ1
~
41.0; IR (KBr):
ν
= 3011, 2925, 2853, 1443, 1377, 1174 cm ; HRꢀMS (ESIꢀTOF): m/z
9
calculated for C21H17NO2SBr [M + H]+: 426.0158, found: 426.0126.
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N-(4-Iodophenyl)-N-(4-(phenylethynyl)phenyl)methanesulfonamide (3ab): Rf = 0.50
1
(hexane:ethylacetate 9:1); white solid; yield 78% (124 mg); mp 202ꢀ203 °C; H NMR (400
MHz, CDCl3): δ 7.97 (d, J = 8 Hz, 1H), 7.92ꢀ7.91 (m, 1H), 7.70ꢀ7.68 (m, 1H), 7.37ꢀ7.28 (m,
8H), 7.19ꢀ7.16 (m, 2H), 2.88 (s, 3H); 13C NMR (100 MHz, CDCl3) δ = 137.5, 136.3, 134.0,
132.5, 131.9, 131.8, 130.2, 129.9, 129.2, 128.6, 127.9, 127.5, 123.6, 117.5, 88.8, 41.0; IR
ꢀ1
~
(KBr):
ν
= 3031, 2923, 2852, 1442, 1373, 1173cm ; HRꢀMS (ESIꢀTOF): m/z calculated for
C21H16O2SNINa [M + Na]+: 495.9839, found: 495.9837.
N-(4-(tert-Butyl)phenyl)-N-(4-(phenylethynyl)phenyl)benzenesulfonamide (3ac): Rf =
1
0.45 (hexane:ethylacetate 9:1); white solid; yield 66% (106 mg); mp 157ꢀ158 °C; HNMR
(400 MHz, CDCl3): δ8.33 (d, J = 8 Hz, 1H), 7.51ꢀ7.45 (m, 5H), 7.32ꢀ7.28 (m, 5H), 7.24ꢀ7.19
(m, 5H), 7.11ꢀ7.09 (m, 2H), 1.35 (s, 9H); 13C NMR (100 MHz, CDCl3): δ 147.6, 138.5,
136.9, 135.4, 133.5, 132.9, 132.2, 131.0, 130.1, 130.0, 128.8, 128.5, 128.3, 127.4, 127.1,
~
127.0, 125.1, 123.4, 116.1, 115.8, 34.8, 31.7; IR (KBr):
ν = 3062, 2962, 1604, 1585, 1460,
1381, 1183 cmꢀ1; HRꢀMS (ESIꢀTOF): m/z calculated for C30H28NO2S [M + H]+: 466.1835,
found: 466.1813.
6-Bromo-9-(methylsulfonyl)-2-phenyl-carbazole (3a'): Rf = 0.55 (hexane:ethylacetate
1
19:1); white solid; yield 6% (6 mg); mp 216ꢀ217 °C; H NMR (400 MHz, CDCl3): δ 8.38 (s,
1H), 8.15 (s, 1H), 8.06 (d, J = 8 Hz, 1H), 8.02 (d, J = 8 Hz, 1H), 7.71ꢀ7.68 (m, 3H), 7.62ꢀ7.59
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(m, 1H), 7.51ꢀ7.48 (m, 1H), 7.42ꢀ7.39 (m, 1H), 3.02 (s, 3H); 13C NMR (100 MHz, CDCl3) δ
142.1, 140.8, 139.4, 137.6, 130.4, 129.1, 128.0, 127.9, 127.7, 124.2, 124.0, 123.3, 120.8,
117.8, 116.3, 113.3, 39.09. HRꢀMS (ESIꢀTOF): m/z calculated for C18H11BrN [M – SO2Me]+
320.0075, found 320.0085.33
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N-(5-Iodo-2',2'',4',4'',6',6''-hexamethyl-[1,1':3',1''-terphenyl]-2-yl)methanesulfonamide
(4): Rf = 0.45 (hexane:ethylacetate 9:1); white solid; yield 77% (69 mg); mp 199ꢀ200 °C;1H
NMR (700 MHz, CDCl3): δ 7.68 (d, 1H, J = 14 Hz), 7.49 (s, 1H), 7.45 (d, 1H, J = 7 Hz), 7.11
(s, 1H), 6.95 (s, 1H), 6.00 (s, 1H{NH}), 2.96 (s, 3H), 2.33 (s, 3H), 2.01 (s, 3H), 1.91 (s, 3H),
1.89 (s, 3H), 1.87 (s, 3H), 1.56 (s, 3H); 13C NMR (175 MHz, CDCl3) δ 137.7, 137.3, 136.7,
136.5, 135.3, 135.2, 135.1, 134.9, 134.4, 133.0, 131.6, 130.4, 128.7, 128.6, 119.1, 87.9, 40.0,
ꢀ1
~
21.2, 20.3, 20.1, 20.0, 19.9, 17.5; IR (KBr):
ν
= 3042, 2913, 1529, 1585, 1483, 1335 cm ;
HRꢀMS (ESIꢀTOF): m/z calculated for C25H29INO2S (M+H) 534.0958, found: 534.0932.
ASSOCIATED CONTENT
Supporting Information
The Supporting Information file contains NMR spectra and crystallographic information.
AUTHOR INFORMATION
Corresponding Author: *pmal@niser.ac.in
ORCID
Saikat Maiti: 0000ꢀ0003ꢀ0951ꢀ3542
Prasenjit Mal: 0000ꢀ0002ꢀ7830ꢀ9812
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Notes
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The authors declare no competing financial interest.
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ACKNOWLEDGMENT
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We thank DST (New Delhi, India) for their support and S. M. thanks CSIR (India) for the
fellowship.
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